Disazo dyestuffs



United States Patent Office 2,861,985 Patented Nov. 25, 1953 DISAZODYESTUFFS Hans Ischer and Lukas Schneider, Basel, Switzerland,assignors, by mesne assignments, to Saul & C0., Newark, N. J., asnominee of Fidelity Union Trust Company, executive trustee under SandozTrust No Drawing. Application March 30, 1955 Serial No. 498,109

Claims priority, application Switzerland December 24, 1952 8 Claims.(Cl. 260-447) The present invention is a continuation-in-partapplication of the co-pending application Ser. No. 398,869, filed onDecember 17, 1953 (now abandoned), and relates to new copperable disazodyestuffs and to the copper and nickel complex compounds thereof.

The new disazo dyestuffs correspond in the metal-free form to thegeneral formula lower alkyl wherein one y stands for OH, the other 3/being OH, -OCH;.,, OCH COOH or COOH, y-R stands for a radical of thebenzene, naphthalene or pyrazolone series, the y of y-R being inortho-position to -azo-, y-R stands for a radical of the benzene series,the y of y-R being in ortho-position to -azo-, and wherein R stands fora radical chosen from radicals of hydroxybenzenes, hydroxynaphthalenesand aliphatic and heterocyclic hy droXy compounds which by reason oftheir containing an enol grouping are capable of coupling. a r

The new disazo dyestuffs are prepared by coupling one mol of the diazocompound of an aminomonoazo dyestuif of the formula lower alkyl whereiny, y-R and y--R have the previously-recited significances, the y of yRand the y of y-R being in ortho-position to -azo-, with one mol of acoupling compound of the hydroxybenzene or hydroxynaphthalene series oran aliphatic or heterocyclic hydroXy compound which by reason of itscontaining an enol grouping is capable of coupling, and, if desired,treating the resultant disazo dyestulf in substance or on the fiber witha copperor nickel-yielding agent. In lieu of dyestuif (II), thecorresponding coppered or nickeled product may be used.

A series of disazo dyestuffs obtainable according to the aforesaid firstprocess embodiment of the present invention can also be obtained bycoupling one mol of the diazo compound of an aminomonoazo dyestuif ofthe formula lower alkyl 1/ I wherein R has the precedingly-indicatedsignificance, and

y-R stands for a radical of the benzene series, the y being inortho-position to --NH and standing for of the Formula II in indirectmanner. To this end, the dyestuffs are dissolved in water, the requisitequantity of sodium nitrite added to the solution, and the latteradjusted to distinct mineral acidity by means of hydrochloric acid. Thecoupling of the obtained diazo compounds with the coupling compounds ofthe hydroxybenzene or hydroxynaphthalene series or aliphatic orheterocyclic hydroxy compounds which by reason of their containing anenol grouping are capable of coupling, is advantageously carried out inalkaline medium.

The coupling of the diazo compounds: of Formula III with the compoundsof the hydroxybenzene, hydroxynaphthalene or pyrazolone series whichcouple in orthoposition to the hydroxyl group, according to theaforesaid second process embodiment, is advantageously carried out inalkaline medium, if desired, in the presence of pyridine or othersimilarly-acting organic bases.

The disazo dyestuffs obtained according to the first process embodimentare obtained as copper or nickel compleX compounds or, like the productsobtained according to the second process embodiment, contain ametallizable ortho ortho dihydroxy azoor ortho hydroxyortho methoxyazoor ortho hydroxy ortho carboxy azo or ortho hydroXy orthocarboxymethoxyazo grouping. The metallizing of the disazo dyestuffs onthe fiber may be carried out according to a single bath process oraccording to an aftermetallizing process. The metallizing in substancemay be carried out by heating the dyestuifs with copper or nickel saltsin weakly acid to alkaline medium, if desired, under pressure and/ or inthe presence of ammonia or organic bases or in a fusion of alkali metalsalts of low molecular aliphatic carboxylic acids. If one of thesubstituents capable of copper or nickel complex formation is themethoxy group, then the metallizing is advantageously carried out withsplitting of this group.

The aminomonoazo dyestuifs of Formula II, employed in the first processembodiment, can for example be obtained by condensing amines of theformula lower alkyl r l I naval-Nero 001cm wherein y and y'-R have thepreviously-indicated significances, followed by coupling of theso-obtained tetrazo compounds on one side with the coupling compounds ofthe hydroxybenzene or hydroxynaphthalene series or aliphatic orheterocyclic hydroxy compounds which by reason of their containing anenol grouping are capable of coupling. This coupling is advantageouslycarried out in weakly alkaline or acid medium.

The disazo dyestuffs metallized in substance according to the presentinvention, as well as the disazo dyestuffs which have been metallized onthe fiber, yield, on cotton and fibers of regenerated cellulose,relatively vivid yel lowish to bluish-red shades of good fastness tolight and to washing. The fastness properties of many of the dyeingsprepared with the disazo dyestuffs of the present invention can also beimproved by an aftertreatment, carried out in the presence of salts ofbivalent copper, With polymeric compounds containing imino or aminogroups, such as are disclosed for example in U. S. Patent No. 2,622,075of December 16, 1952.

The following examples further illustrate the invention Without,however, limiting the same; in these examples,

the parts and percentages are by weight and the temperatures are indegrees Centigrade.

EXAMPLE 1 51.2 parts of the monosodium salt of the aminomonoazodyestufli-obtained by acid coupling of diazotized 1- hydroxy 2 amino 6chlorobenzene 4 sulfonic acid with 1-methoxy-3-aminobenzene, acylationof the resultant aminomonoazo compound with3-methyl-4-nitrobenzene-l-carboxylic acid chloride, and reduction of thenitro group to the amino groupare dissolved in 900 parts of water. 24parts of aqueous sodium nitrite solution of 30% strength are added tothe solution, which is then cooled by means of ice to a temperature ofafter which 40 parts of hydrochloric acid of 30% strength are quicklyrun in. After stirring for three hours at a temperature of 15,diazotization is ended; the resultant suspension is then combined in thepresence of aqueous sodium carbonate with an aqueous solution of 32parts of the sodium salt of2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid. The new disazodyestuff is formed instantaneously. It is precipitated from the warmsolution by means of sodium chloride and is then filtered off and dried.It is a dark powder which dissolves with red coloration in Water andwith bluish red coloration in concentrated sulfuric acid.

In order to convert the said dyestuff into its copper complex compound,82.6 parts of the disodium salt of the disazo dyestuff are dissolved in2060 parts of water. To the resultant solution, there are graduallyadded at 90 250 parts of an arnmoniacal copper oxide solution,

4 containing 25 parts of crystalline copper sulfate and parts of aqueousammonia solution of 25% strength. The mass is then heated to boiling andmaintained at this temperature under reflux for six hours. Thethus-prepared copper-containing disazo dyestui f is precipitated fromthe metallizing solution by meansof sodium chloride and is then filteredoft and dried. It corresponds to the formula and dyes cotton and fibersof regenerated cellulose in red shades with good fastness to light andto washing.

EXAMPLE 2 OHa HO3S- NHCOCH;

and dyes cotton and fibers of regenerated cellulose in bright red shadesof good fastness to light and washing.

Table 1, which follows, sets forth additional metalcontaining disazodyestuifs which can be prepared after the manner described in Examples 1or 2 and which possess properties similar to the product of Examples 1and 2. They correspond in the metal-free form to the formula whereinsymbols A and B represent the radicals set forth in the table and xrepresents the enumerated substituents.

Table 1 Shade of Example N o. A=Radical of- B=Radical of 1 Metal Dyeingon Cotton 3 1 hydroxy 2 amino 6 chloroben- 2 benzoylamino 5 hydroxynaph-H Cu Red.

zene 4 sulfonic acid. thalenc 7 sulionic acid. 4 do 2 carbethoxyamino 5hydroxy- -H On Do.

naphthalene 7 sulfouic acid. 6 do 2 (4 -iumary1an1in0) benzoylamino- HCu Do.

5 (l1iydr0xynaphthalenc 7 sulfonic act 6 1 hydroxy 2 amino 4 chloroben-2 acetylamino 5 hydroxynaphtha- H Ni Do.

zene 6 sulfonic acid. lene 7 a sulfonic acid. 7 1 hydroxy 2 aminobcnzene4 sul- 2 benzoylamino 5 hydroxynaphtha- H Cu Do.

tonic acid. lene 7 sultonic acid. 8 do 1 chloro 2 beuzoylamino 5 hy- HCu Do.

droxynaphthalene 7 sulfonic acid. 9 do 2 (4 acetylamino) benzoylamino- HCu Do.

5 gydroxynaphtha1ene 7 sulionic aci 10 1 hydroxy 2 aminobenzcne 4 sul- 2benzoylamino 5 hydroxynaphtha H Cu Do.

fonc acid (2 carboxy) phenylalene 7 sulfonic acid. m1 e. 11 1 hydroxy 2amino 6 chlorobcn- 2 acetylamino 5 hydroxynaphtha- OH; Ni Do. lene 7sulionic acid.

zene t sulionic acid,

. Shade of Example N o. A=Radical of- B=Radica1 ofz: Metal Dyeing onCotton 12 1 hydroxy 2 aminobcnzene 4 5111- 2 benzoylamino 5hydroxynaphtha- OH 011 Red.

ionic acid. lene -7 sulfonic acid. 13 do 1 ChlOlO 2 acctylamino 5hydroxy- OH Cu Do. naphthalene 7 sulfonic acid. 14 d l 2 acetylaminohydroxynaphtha- -OOH Cu Bordeaux:-

lene 7 sulfonic acid. red. 15; 1 hydroxy 2 aminobenzene 4 sul- 2bcnzoylamino 5 hydroxynaphtha- -H Cu Red,

ionic acid amide. lcne 1,7 disulfonic acid. 16 do 2 carbethoxyamino 5hydroxynaph- H Cu Do.

thalene 1,7 disulfonic acid. d0 2 (2 carboxy) benzolyamino 5 H Cu Do.

hygroxynaphthalcne 7 sulfonic aci .do 2 (4' amino) benzoylamino 5 -H CuDo,

hygroxynaphthalcne 7 sullonic aci 1 hydroxy 2 aminobenzene- 4 sul- 2bcnzoylamino 5 hydroxynaph- H 011 D0.

ionic acid methylamide. thalene 1,7 disulfonic acid. 1 hydroxy 2 amino 6acetylami- 2 acetylamino 5 hydroxynaphtha- H 011 Do.

nobenzene 4 snlfonic acid. lene 7 sulfonic acid. 1 hydroxy 2 amino 4methylsul- 2 benzoylamino 6 hydrownaphtha- -H Ni Do.

fonylbenzene. lane -7 -sulfonic acid. 1 hydroxy 2 aminobenzene 4 3111-do H Cu Do,

fonc acid (2 hydroxy) ethylam1 e. 1 hydroxy 2 aminobenzenc 4 5111- 2carbcthoxyamino 5 hydroxynaph- H Cu Do.

fonic acid phenylamidc. thalcne 1,7 disuliomc acid. 1- hydroxy 2 amino 6bcnzoylamido -E[ On Do nobenzene 4 sulfonic acid. 1 hydroxy 2aminobenzene 4 suld0 H Ou Do.

Ionic acid dimethylamide. 26 l hydroxy 2 aminobenzcne 4 sul- 2acetylamino 5 hydroxynaphtha- H Cu Do,

fonc acid (N methyl) phenylalenc 1,7 disulfonic acid. m1 e. 27 1 hydroxy2 aminobenzene 2 carbethoxyamino 5 hydroxynaph- -H Cu D0.

thalcne 1,7 disulfonic acid. 28 .do 2 (4 amino) benzoylarnino 5 H Cu Do,

hydiroxynaphthalene 1,7 disulfonic aci 29rd... .do 2 sulfoacetylaminohydroxynaph- -OH- Cu D thalene 7 sulionic acid. 30 1 hydroxy 2aminobenzene 4 sul- 5 hydroxy 7 sulfonaphthyl (2) car- -H 011 Do,

ionic acid. bamic acid (4 acetylamiuo) phenylamide. 31 1 hydroxy 2 amino6 chlorobendo -H Ni Do, zenc sulionic acid. 32 1 hydroxy 2 aminobenzene4 sul- 6 hydroxy 7 sulfonaphthyl (2) car- -H Cu D fonicacid. bamicacid-benzylamide. '33 ..do 5 hydroxy 7 sul.fonaphthyl(2) car- H Cu Dobamic acid-phenylamidc. V 34 do 5 hydroxy 7 sulfonaphthyl(2) car- -H OuDo.

bamic acid (4 butyrylamino) phenylamide. '35..- do 5 hydroxy 7su1fonaphthy1(2) car- --H on Do.

, bamic acid-cyclohexylamide.

'The following is a formula of a representive product of the foregoingexamples:

EXAMPLE 7 O- C11 (I) (EH H O OaH H EXAMPLE 3 6 The copper-containingdisazo dyestutf described in Example 1 can also be obtained bysubjecting the 51.2

parts of the monosodium salt oi": the aminomonoazo dyestud employed inExample 1 to demethylating coppering according to the data of Example 1,then diazotizing the resultant copper complex compound and combining theproduct, in the presence of excess sodium carbonate with an aqueoussolution of 32 parts of the sodium salt of l-acetylamino 5hydroxynaphthalene 7 sulfonic acid. The thus-obtained copper-containingdisazo dyestuff is salted out, filtered off and dried.

EXAMPLE 37 A neutral suspension, cooled to a temperature of 8-10,

(IJOOBI (3H3 HOaS- NHCOOCzHs The aforementioned diazomonoazo suspensionis obtained by stirring 28.5 parts of 1-(4'-amino-3-methyl)-benzoylamino 4 aminobenzene 3 carboxylic acid into 800 parts of icewater, adding 50 parts of hydrochloric acid of 30% strength to theresultant suspension, and then at adding 46 parts of aqueous sodiumnitrite solution of 30% strength. A solution of 33.3 parts of the sodiumsalt of 2-carbethoxyamino-S-hydroxynaphthalene 7 sulfonic acid in 400parts of Water is run into the tetrazo solution, the temperature of thecoupling mass adjusted to 8 to 10, and then within the course of onehour approximately 20 parts of sodium bicarbonate added theretoportionwise. After the resultant mass has been adjusted to neutrality,stirring is continued for two more hours at 8-10. Coupling takes placeonly at the diazo group situated on the benzoyl radical. The resultantdiazomonoazo compound separates in the form of orange-red crystals.

EXAMPLE 38 The neutral suspension of the diazomonoazo intermediateobtained according to the second paragraph of EX- ample 37 is run in thecourse of 1 hour into a solution of 27.5 parts ofl-phenyl-3-methyl-5-pyrazolone-3-sulfonic acid, 10 parts of sodiumcarbonate, 300 parts of pyri- V V dine and 500 parts of water at Thedisazo dyestuff thus formed is precipitated while still warm by means -8of sodium chloride and then filtered off. For converting into the coppercomplex compound, the humid filter cake is first dissolved together with25 parts of crystalline sodium acetate in 1500 parts of water at 80-85.Then a 20% copper sulfate solution is added dropwise until copper ionscan be detected in the filtrate of a salted-out sample. The resultingcopper-containing disazo dyestuff is precipitated as a sodium salt bythe agency of sodium chloride, and subsequently filtered off and dried.It dyes cotton and fibers of regenerated cellulose in red shades of goodfastness to light and washing. The washing fastness of the dyeings isenhanced by after-treatment with copper salts on the fiber.

Table 2 sets forth additional disazo dyestufls which can be preparedafter the manner set forth in Example 37 and which possess propertiessimilar to those of the product of Example 37. These disazo dyestuffscorrespond in the copper-free form to the formula 1! Y CH3 (VII) whereinsymbols A and B represent the radicals enumerated in the table and yrepresents the substituents therein set forth. The copper-containingdisazo dyestufi of Example 59 is prepared according to the methoddescribed in Example 38.

Table 2 Shade on Example A=Rad1cal of B=Radical of- 11= Use as Cotton, N(Joppcred 39 1-(4-hydroxy)-pheny1-3-methyl-5- 2-carbethoxyamino-fi-hydroxy- O00H Aftercoppering Scarlet red.pyrazolone-3-carboxylic acid. naphthalene-7-sulionic acid. dyestufl. 403-methyL5-pyrazolone 2-benzoylamino -5-hydroxynaph- OOOH .-..do Dothalene-1,7-disulfonic acid. 41 1-[4'-(4"-amino)-phenyl]-phenyl-3- doCOOH do Do,

methyl-5pyraz0lone. r r 42 1 [4 (4 acetylamino) phenylj .....do O0OH .doDo.

phenyl-3-methyl-5-pyrazolone- 2-sulfonic acid. l r r 7 7 r 43l-phenyl-3-methyl-5-pyrazolone-3- 2-acetylamino-5-hydroxynaphtha- COOH..-..d0 Do.

sulfonic acid amide. V lene-7-sulionic acid. 44 1- (4'-chloro)-phenyl-3-mcthyl-5- 2- 1cctylamino-5-hydroxy'naphtha- COOH .do....; Do.

py-razolone. 1enc-1,7-disulfonic acid. 45 1-(3"ch10ro)-pheny1-3-methyl-5- 2-carbethoxyamino-5-hydroxy- COOH ...-.d0D0.

pyrazolone. naphthalene-1,7-disulfonic acid. 46l-phenyl-3-methyl-5-pyrazolone- Z-bcnzoylamino -5-hydroxynaph- COOH doDo.

3-sulfonic acid. thalene-7-sulionic acid. 47--.l-phenyl-3-mcthyl-5-pyrazolone- ....do COOH .do Do.

4-snlfonic acid. 48 1,3-dihydroxybenzenei-carboxylicl-chloro-2-carbethoxyamino-5-hy- COOH ..do Brownacid. dro xyn aphth alon e,-7 -sulfonic red.

ac 49.-. Z-acetylamino-5-hydroxynaphtha- 2-acetylamino-5-hydroxynaphtha-COOH d0 Ruby-red.

Iene-Tsulfonic acid. lene-7-sulfonic acid. 50 2 carbethoxyamino 5hydroxy ..-..d0 COOH ..d0 Do,

naphthalcne-7-sulfonlc acid. 51.... 2-(3-methyl-4-arnin0)-benzoyl- ..doO0OH .-.-do Do.

amino-fi-hydroxynaphthalene-7- sulfonic acid. I 621-hygroxynaphthalene-4-sulfonic ..-.do --OOOH .d0 Bordeauxaci re 53...-2-benzoylamino-5-hydroxynaph- -COOH ----.do D0,

thalenc-7-sulfcnic acid. 54. 2 hydroxynaphthalene 4 sul- -.do COOH -.doDo.

ionic acid. 55... 1 hydroxynaphthalcne 3,8 di- 2 (2 chloro) benzoylamino5- -COOH -.--.do Do.

sulfomc acid. hydlroxynaphthalene -7-sulfonic aci 66.2-hydroxynaphthalene. 2 carbethoxyamino 5 hydroxydo Ruby-red,

naphthalene-1,7-disulfonic acid. 57....------- 2 hydroxynaphthalene 3cardo .do Do.

boxylic acid amide. 58.....------ 2-benzoylamino-5-hydroxynaph- --.doCOOH -.--.do Do.

thalene-7-sulionic acid. 59 2-benzoylamino -5-hydr0xynaph- ----.do COOHCopper complex. Do.

thalene-1,7-disulfonic acid. 60. 2 -benzoylarnino -5 -hydroxynaph- 2sulfoacetylamino 5 hydroxy- CO OH Aitercoppering D0.

thalene-Wsulfonic acid. naphthalene-7-sulionic acid. dyestufi. 61. 2acetylammo 5 hydroxynaph- 2-benzoylamino -5-hydroxynaph-Bordeauxthalene-7-sulfonic acid. tiialene-l,7-disu1fonic acid. re 62. 2(4 -fumarylan1ino) -bcnzoylami- ---..do Do,

no-5-hydroxynaphthalene-7-sultonic acid. 63. 1- phenyl- 3f methyl 5pyrazolone- 5 hydroxy-7-sulfonaphthyl (2) Scarlet- 3 -sullon1c acid.carbamic acid- (4-acetylamino) red.

. phenylamide. 64- l-phenyl-3-methyl-5-pyrazolone-5-hydr0xy-7-sulfonaphthyl(2)-car- Do.

3-su1foruc acid-methylamide. bamic acid-propylamide.

Shade on Example A=Radical of- B=Radica1 oty= Use as Cotton, N o.Ooppered (3) (5) 65. Z-acetylamino-5-hydro rynaphtha- 5 hydroxy 7sulfonaphthyl (2) COOH Attercoppering Scarlet-red.

lene-7-sulfonic acid. carbamic acid-methylamide. dyestuff. 66l-hydroxynaphthalene- 3,8 -disul- 6 hydroxy 7 sulfonaphthyl (2) -C OOH.do Bordeaux tonic acid. carbamic acid (4 benzoylami red. no)-phenylamide. 67. do 5 hydroxy 7 sulfonaphthyl (2) COOH do Do;

carbamic acid-(4-phenyl) -phenamide. 2-benz ylamino.-6-hydroxynaph 5hydroxy 7 sulfonaphthyl (2). OH do Do.

thalene-7sulfonic acid. carbamic acid-amide.

1-phcnyl-3-methyl-5-pyrazolone- 2-crotonylaminc-5-hydr0xyriaph 3sulfonic acid methylamide. thalene-7-sulfonie acid.

70 3-phe11y1 5-pyrazol0ne Z-acetylamino-5-hydroxynaphtha= C OOH do -Doi1ene-7-sulfoi1ic acid. 7l 1-phenyl-3-methyl -5-pyrazolonedo -OOH d0 Do 3-sulfonic acid. COOH 72. do 4 acetoaeetylammo 4 nitrostil -00 OH .doYellow.

bene-2,2'-disulfonic acid. 73.2-acetylami11o-5-hydroxynaphthal-liydroxyi-phenylbenzene COOH -do Red.

1ene-7-suliom'c acid. 74. d0 aeetoacetylarninobenzene.- --COOH .do Do.75. 2-benzoylamino-5-hydroxynaph- 1-phenyl-3-methyl-5-pyrazolone- COOIE[.do D0.

thalene-7-sulfonic acid. 3-sulfonic acid-methylamide.

The following is a formula of a representative product and dyes cottonand fibers of regenerated cellulose by of the foregoing examples: theaftercoppering process in red shades of good fastness EXAMPLE 43 tolight and to washing.

N-C-OH N/ (F0012: OH; Hogs Nnoocm l o-oN=N- N11oo 1\r=1s- NH: I

EXAMPLE 76 45 Table 3 sets forth additional disazo dyestufis which canbe prepared after the manner described in Example 76 and which possessproperties similar tothose of the product described in Example 76. Thesedisazo dyestuffs correspond in the copper-free form to the formula 40.4parts of the aminomonoazo dyestuft-prepared by coupling diazotizedZ-amino-S-nitrobenzene-l-carboxylic acid with 1-hydroxy-4-methylbenzene,reducing the nitro group to the amino group, acylating the obtainedaminomonoazo compound with 3-methyl-4-nitrobenzene-1-cary CH! boxylicacid chloride and again reducing the nitromonciazo1 7 com ound to theaminomonoazo dyestuffare disso ve in tlie presence of sodium hydroxidein 1000 parts of 7 water, diazotized after the manner set forth inExample v11) 1, and coupled in the presence of sodium carbonate with Ian aqueous solution of 423 parts of 2-benzoylamino-5- wherein symbols Aand B represent the radicals enuhydroxynaphthalene-1,7-disu1fonic acidand. 26.3 parts of oriented in the table and y represents thesubstituents an aqueous sodium hydroxide solution of 30% strength.theremset forth.

The. disazo dyestuff is precipitated from the warm reac- Themetal-containing disazo dyestuffs of Examples 83',

tion solution by means of sodium chloride and is then 84; 87 and 88 areprepared according to the method given filtered oil and dried. Itcorresponds to the formula in Example 38, whereby, 1n the caseofnickehng, the cop on 00011 (3H3 HOaS- -NH-oo l i a I no and dissolveswith yellowish red coloration in water and" per sulfate used in thisexample is replaced by nickel with bluish red coloration in concentratedsulfuric acid sulfate.

Table 3 Shade on Example No. A--Radical of B=Radical f:- y= Use asCotton,

* Coppered 77. 1-methyl-4-hydroxybenzene. Z-carbethoxyamino-o-hydroxy---OO OH Aftercoppering Red.

. naphthalene-7-sulionic acid. dyestufi.

78- do Z-acetylamino-fi-hydroxynaph- O O OH do Do.

thalene-7-sulfonic acid.

79. dn 2-benzoylamino-5-hydroxynaph- 00 OH -do Do.

thalene-7-sulfonic acid.

80 do 2 (4-amlno)benzoylamino-ti-hy COOH do Do.

droxynaphthalene- 7 s 111 to 1110 ac 81 1,3-dimethylt-hydroxybenzene..Z-carbethoxyamino-fi-hydroxy-' GOOH do Do.

naphthalene-7-sulfonic acid.

82- 2-benzoylamino-fi-hydroxynaph- OOOH do Do.

thalene-1,7-disulfonic acid.

83 l-methyM-hydroxybenzene. 2-carbeth0xyamino-5-hydro xy- GO OH Coppercomplex. Do.

naphthalene-1,7-disulf0nic acid.

84.... do 2-sulfoacetylamino-5-hydroxy- GOOH .do D0.

naphthalene-7-sulfonic acid.

85. .do Z-benzoylamino-5-hydroxynaph- OH AftercoppermgBlulshtha1ene-7-sulfonic acid. dyestufi. red.

86- do Z-acetylamino-b-hydroxynaph- OH .d0 D0.

thalene-7-sulfonic acid.

87... 2-su1foacetylamino-fi-hydroxy- OH Nickel complex. Do.

naphthalene-7-sulfonic acid.

88 1,3dimethyH-hydroxybenzena. 2-carbethoxyamino-5-hydroxy- OH do Do.

naphthalene-1,7-disulfonic acid.

89.... --.'.do 5-hydroxy-7-sulfonaphthyl(2) OH AftereoppermgBordeauxcarbamic acid-(4-acetylamil10)- dyestufi. red. phenylamide.

90 l-methyl-4-hydroxybenzene. rln Yellgwre 91.....Z-hydroxy-naphthalene... o-hydroxy-7-su1fonaphthy1(2)- Bordeauxcarbamicacid-methylamide. re

E QUMPLE 92 90 parts of the disazo dyestufi are converted into the 58.6parts of the aminomonoazo dyestufiobtained by coupling diazotized1methoxy-2-amino-5-nitrobenzene- 4-sulfonic acid with2-hydroxynaphthalene-4-sulfonic acid, reducing the nitro group to theaminogroup, acylating the resultant aminoazo compound with 3-methyl-4-nitrobenzene-l-carboxylic acid chloride and again reand dyes wool andfibers of regenerated cellulose in bordeaux-red shades of good fastnessto light and to washing.

copper complex compound after the manner described in Example 1. Thethus-obtained copper complex compound corresponds to the formula GHa H.08

NHCO 00 K ducing the nitro group to the amino group-are dissolved Table4 sets forth additional metal-containing disazo in 1200 parts of waterwith the aid of 15 parts of sodium dyestuffs which can be prepared afterthe manner set carbonate. To the resultant solution there is then addedforth in Example 92 (nickeling as set forth in Example a solution of 7.5parts of sodium nitrite in 50 parts of 2). They possess propertiessimilar to those of the water and the mixture is then rapidly acidifiedwith 50 product of Example 92. These dyestuffs correspond in parts ofhydrochloric acid of 30% strength, while stirring the unmetallized stateto the formula V at a temperature of 510. After stirring for three hoursat 10-15 the diazotization is ended. The diazo suspen- OOHS E sion iscombined with a solution of 32 parts of2-carbethoxyamino-5hydroxynaphthalene-7-sulfonic acid, ex- AN N cesssodium carbonate and 400 parts of water. The new so H (Wm disazodyestufi forms instantaneously. It is precipitated from the warmcoupling solution by means of sodium chloride and is then filtered ofland dried.

wherein symbols A and B represent the radicals enumerated in the table.

Example Shade of No. A=Radicalof- B=-Radical.of Metal Dyeing n Cotton96.; 2-hydroxynaphthalene-4- 2-(4-fumary1amjno)-,benzo- OuBordeauxsulfonic acid. ylamino -5-hydroxynaphred. 1 thalene-7-sulfonicacid. 97 .do 2-fumarylamino-5rhydroxy- 011 Do.

naghthalenoJ-sulfonic act 98 .do 2- (2'-carboXy)-benzoylami- N1 D0;

' no-fi-hydroxynaphthalene-7-snlfonic acid. 99 2-hydroxynaphthalene-6-2-benzoylamino-5-hydroxy- 011 Do.- sulfonic acid. nighthalene -7-sulfonic ac, V l 100 1-hydroxynaphtha1ene-4- 2-carbethoxyamino-5-hy CuDo.

sulfonic acid. droxynaphtha1ene-1,7-

disultonic acid. 101 2-acetyIamino-5-l1ydroxyl. do Cu Do.-

naighthalenefl-sulfonic ac 102. 2-(4,-fumary1amino)-ben- -do 011 Do.

zoylamino5-hydroxynaphthaleneJ-suifbnic aci 103 l-methyli-hydroxyben---do Ou Red.

zene.

EXAMPLE 104 equivalent quantity of the 2-(4-amino-3-methyl)- 42.6 partsof the aminomonoazo dyestufi of the formula GOONa OH C'Hs NHOOG-NH:

'( Ha (IX) are diazotized after the manner described in Example 1 andare combined in the presence of excess sodium carbonate with an aqueoussolution of 48 parts of 2-benzoylamino5-hydroxynaph'thalene-1,7-disulfonic acid sodium salt. The resultantdiazo dyestuif separates out in crystalline form. It is filtered oifwith the aid of suction and is dried. It corresponds to the formulaGOONa OH CH; HOtS and is a dark powder which dissolves with redcoloration in water and with bluish red coloration in concentratedsulfuric acid. It dyes cotton and fibers of regenerated cellulose by theaftercoppering process in red shades of good fastness to light and towashing.

EXAMPLE 105 If, while otherwise proceeding according to Example 104, the48 parts of 2-benzoylamino-S-hydroxynaphtha- 1ene-1,7-disulfonic acidsodium salt are replaced by the Eaglesbenzoylamino-S-hydroxynaphthalene-7-sulfonic acid sodium salt, acopperable disazo dyestufl? with similar properties isobtained.

EXAMPLE 107 51.4 parts of the aminomonoazo dyestutf of the formula arediazotized after the manner described in Example 1.

In order to convert the said dyestuff into its copper complexcompound,82.8 parts of the disodiumsalt of the disazo dyestulf and 27parts of crystalline sodium acetate are dissolved in 2000 parts ofwater. To the resultant solution, there is gradually added at 85 anaqueous solution containing 25 parts of crystalline copper sulfate,

The mass is then kept at a temperature of 80-85 during half an hour. Thethus-prepared copper-containing disazo dyestuff is precipitated by meansof sodium chloride and is then filtered 01f and dried. It corresponds tothe formula CH3 H018 NHOOCH:

solution are added portionwise to the bath. The dyed ,material is thenpermitted to cool in the bath at 50 in 25 consisting of hydrogen,methyl, methoxy and --SO H, one the course of 15-20 minutes after whichit is rinsed with .ceding example. In this case, however, anaftertreatment and dyes cotton and fibers of regenerated cellulose inwherein one y stands for OH, the other y being a membordeaux-red shadeswith good fastness to light and to her selected from the groupconsisting of OH, OCH;,, washing. OCH COOH and COOH, yR stands for aradical selected from the group consisting of a radical of the benzene,naphthalene and pyrazolone series, the y of yR being in ortho-positionto -azo-, yR stands for a radical of the benzene series, the y of yRbeing in ortho-posi- EXAMPLE 108 0.1 part of the disazo dyestufiobtained according to Example 76 is dissolved in 300 parts of water.parts of prewetted cotton cloth are dyed in this bath, which is tion to-azo-, and wherein R stands for a radical selected initially at atemperature of approximately and is from the group consisting ofhydroxybenzene, hydroxyheated to boiling in the course of thirty minutesand 10 naphthalene, enolic pyrazolone and enolic fi-ketocarfinallymaintained at boiling temperature for fifteen minboXylic arylamideradicals. utes. In the course of the dyeing process, 3-4 parts of 2. Adisazo dyestuff which corresponds in the metalanhydrous sodium sulfatein the form of a 10% aqueous free form to the formula wherein x standsfor a member selected from the group y stands for OH, the other y beinga member selected water and subjected to an aftertreatment with copperfrom the group consisting of OH, OCH sulfate or with a cation-activecopper complex compound -OCH COOH and COOH, z stands for a membersewhich, if desired, may be basic. lected from the group consisting ofhydrogen, chlorine EXAMPLE 109 30 and --SO H, acyl is a carboxylic acidacyl group, and

, y-R stands for a radical selected from the group eon- Disalo deystufisacwl'ding t0 the Present invention sisting of a radical of the benzene,naphthalene and pyraz- Which are coppered in substance, may also be usedfor olone series, the y of y-R being in ortho-position to the dyeingcotton cloth after the manner described in the prerespective azo group.

3. The copper complex compound of a disazo dyestufi with copper sulfateis superfluous. which corresponds in the metal free form to the formulaCHs H0 8 NH.acyl

Also the disazo dyestuffs which are nickeled in substance, are dyed inthe same manner, an aftertreatment of the dyeings being superfluous.

Having thus disclosed the invention, what is claimed is:

1. A member selected from the group consisting of a disazo dyestuff andthe copper and nickel complex compounds thereof, which dyestuffcorresponds in the metalfree form to the formula consisting of hydrogen,methyl, methoxy and SO H, one y stands for OH, the other y being amember selected from the group consisting of OH, OCH OCH COOH and COOH,z stands for a member 'selected from the group consisting of hydrogen,chlorine and --SO H, acyl is a carboxylic acid acyl group, and y-Rstands for a radical selected from the group conrower alkyl sisting of aradical of the benzene, naphthalene and pyrazolone series, the y of yRbeing in ortho-position to the y-RazoRr-NHOO respective azo group.

4. The disazo dyestufi which corresponds to the formula CH3 HOaS 5. Thedisazo dyestufi which corresponds to the formula NHC OCH;

CH3 HO S wherein x stands for a member selected from the group 7 6. Thedisazo dyestufi which corresponds to the formula I C OOH I N OIL H0 8NHO 00113 7. The disazo dyestufi which corresponds to the formula (DH0001: :11, H0;S- NHCOQ 8. The disazo dyestufi which corresponds to theformula (|)CP (I) CH3 HOaS- NHCOCH:

References Cited in the file of this patent UNITED STATES PATENTS

1. A MEMBER SELECTED FROM THE GROUP CONSISTING OF A DISAZO DYESTUFF ANDTHE COPPER AND NICKEL COMPLEX COMPOUNDS THEREOF, WHICH DYESTUFFCORRESPONDS IN THE METALFREE FORM TO THE FORMULA